CN109593465A - A kind of organic silicon rubber material of room curing and high temperature resistant and its preparation method and application - Google Patents
A kind of organic silicon rubber material of room curing and high temperature resistant and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of organic silicon rubber material and its preparation method and application of room curing and high temperature resistant, which has low cost, room temperature curing, high temperature resistant, good processing performance, tensile property and adhesive property.The resistance to 350 DEG C of high temperature silicone rubber materials of the room temperature curing are made of two-component, wherein component A is basic sizing material, specifically include that the hydroxy-end capped polysiloxanes containing different functional groups for basic glue, using the pretreated precipitated silica of a certain amount of inorganic agent, optionally a certain number of silicone resin, and cooperate certain high temperature resistant additive；B component is that polysilazane room temperature curing agent matches a certain amount of catalyst composition.The resistance to 350 DEG C of high temperature silicone basis materials construction technology of the room temperature curing is easy, is the desired matrix material for preparing elastic adhesive sealing material, elastic thermal protection coating.
Description
Technical field
The present invention relates to a kind of organic silicon rubber material and its preparation method and application of the resistance to 350 DEG C of high temperature of room temperature curing,
Belong to high temperature resistant elastic material and its preparation technical field.
Background technique
Organic silicon rubber material is because that it is with the characteristics such as good heat resistance, cold resistance, weatherability, ageing-resistant is extensive
The elastic material matrix as resistance to 250 DEG C of high temperature, and with the development of national economy, to the organic silicon rubber of resistance to higher temperature
Material proposes urgent need, this just needs to be modified organic silicon rubber material.Organic silicon rubber material is at high temperature
Degrade failure mechanism and its complexity, with its used in organosiloxane molecular structure, reinforced filling structure and surface characteristic, resistance to height
The structure of warm filling-material structure and various auxiliary agents has relationship.Therefore, how to improve the high temperature resistance of organosilicon material is one
The research work for needing system to carry out.
In addition, the cost effective main trend for being it and developing of material, needs in organic silicon rubber material using a large amount of
White carbon black as reinforced filling, and as heat-resisting material in use, generally select higher cost fume colloidal silica, and
Precipitated silica at low cost causes heat resistance poor because of its architectural characteristic.
Summary of the invention
In order to overcome the above problem, the present invention provides a kind of room curing and high temperature resistant silicone rubber material and preparation side
Method and application, the molecular structure in the organic silicon rubber material for organic silicon rubber are modified, and keep it easy at high temperature
It has an effect with high temperature resistant filler, the block of formation holding certain mechanical properties, rather than dusting, it reduces to Effect on Mechanical Properties
The use of huge carbon forming agent；Precipitated silica added with low cost is as reinforced filling；Polysilazane is added simultaneously to help
Agent may be implemented the organic silicon rubber material in the solidification of room temperature, effectively inhibit the degradation of organic silicon rubber strand, thus
Make its resistance to 350 DEG C of high temperature, also there is good processing performance, tensile property and adhesive property, moreover, the preparation method
Simply, it is suitable as the organic silicon rubber basis material of elastic adhesive sealing material, elastic thermal protection coating, is widely used.
The invention provides the following technical scheme:
The first aspect of the present invention provides a kind of room curing and high temperature resistant silicone rubber material, the rubber material packet
Sizing component A, crosslinking and curing agent B component are included, wherein component A includes: basic glue, white carbon black, high temperature resistant additive, described
Basic glue is hydroxy-end capped polysiloxanes；B component includes polysilazane, catalyst；
The hydroxy-end capped polysiloxanes has the following structure:
Wherein, R1And R2It is identical or different, it is independently from each other methyl, ethyl, phenyl, vinyl, itrile group, trifluoropropyl
Base, nitrile propyl, and it is not simultaneously selected from methyl；X and y is the integer between 0~1000, and is not simultaneously 0.
Preferably, x and y is the integer between 20~700.
Preferably, the molecular weight of the polysiloxanes is 1000~100000, and preferred molecular weight is 2000~60000.
According to the present invention, in the component A, hydroxy-end capped polysiloxanes can be single polysiloxanes, can also be with
Be two or more different structure, different molecular weight polysiloxanes carry out matching use, wherein molecular weight 1000~
Hydroxy-end capped polysiloxanes dosage in 10000 ranges is in 60~100 mass parts, preferably 70~90 mass parts, molecular weight
The dosage of hydroxy-end capped polysiloxanes in 20000~100000 ranges is 40~0 mass parts, preferably 30~10 mass
Part.By the matching of different structure, the polysiloxanes of different molecular weight, the cross-linked network of optimization can be formed, to ensure material
The mechanical property of material.In addition, by introducing carbon containing organic group in the molecular structure of hydroxy-end capped polysiloxanes, to have
Machine silastic material provides have been ensured organic to largely reduce the use of carbon forming agent at high temperature blocking required " carbon source "
The moulding processability and mechanical behavior under high temperature of silastic material.
It according to the present invention, further comprise the organosilicon tree containing D, T, Q structure of following group end capping in the component A
Rouge: one or both of hydrogen, methyl, vinyl, phenyl, methoxyl group and ethyoxyl, illustratively, the organic siliconresin by
Two functional silanes, trifunctional silane and tetrafunctional silane are prepared through hydrolytic condensation.Organic siliconresin is introduced in the component A,
The cross-linked network structure of abundant organosilicon material especially exists to further promote the mechanical property of organic silicon rubber material
Mechanical property under high temperature.
According to the present invention, in the component A, white carbon black is modified dose of treated white carbon black.For example, modified dose
The precipitated silica of processing.Wherein, the precipitation method are prepared by the hydrolysis process well known by persons skilled in the art by silicate
It obtains, there are a large amount of hydroxyls on surface.The modifying agent is silazane or silicone compounds, such as 3wt%~
The combination of one or more of the following modifying agent of 10wt%: hexamethyldisilazane, contains hexamethyl cyclotrisilazane
Hydrogen polysiloxanes, hydrogeneous polysilazane, containing vinyl polysiloxane, polysilazane containing vinyl, octamethylcy-clotetrasiloxane, contain
Hydroxyl polysiloxane.Using the precipitated silica after modifier treatment, the preparation cost of the component can be reduced, due to modification
The hydroxy radical content on treated white carbon black surface substantially reduces, not will lead to organic silicon rubber material generate viscosity increase severely, structure
Phenomena such as change, will not leading to the organic silicon rubber material, processing performance is deteriorated in the construction process, more will not influence organic
The heat resistance of silastic material.
According to the present invention, in the component A, high temperature resistant additive is selected from iron oxide, iron hydroxide, ferric oxalate, alkoxy
Iron, Organosilylferrocene, titanium oxide, zinc oxide, zinc carbonate, cerium oxide, vermiculite, sepiolite, cagelike structure silsesquioxane, carbon
The a combination of one or more of borine (such as hydrogeneous carborane), silicon nitride, silicon carbide, boron nitride.It is introduced in component A
High temperature resistant additive further promotes the high temperature resistance of organosilicon material using the characteristic of its high-temperature oxydation.
According to the present invention, in the B component, polysilazane is used as room temperature curing agent.The polysilazane is without spy
Other restriction can be known in the art polysilazane, illustratively, as disclosed in Chinese patent literature CN1101055A
Polysilazane；Also as applicant submit on the same day it is entitled " a kind of room temperature curing agent of organosilicon material resistant to high temperature,
The Chinese patent of preparation method and application ", is incorporated herein in its entirety in the application, as present disclosure.
Preferably, the viscosity of the polysilazane at room temperature is 200~2000cps, preferably 500~1500cps.
Preferably, the molecular weight of the polysilazane is 200~60000, preferably 500~15000.
According to the present invention, in the B component, catalyst is selected from one of organotin or organic titanium compound or two
The combination of kind, for example, dibutyltin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tins, two acetic acid, two fourth
Ji Xi, dialkyl tin dimaleate, two mercaptan tin alkyls, mercaptan dioctyl tin, butyl titanate, the metatitanic acid tert-butyl ester, acetyl
The single compound of acetone titanium etc. or its chelate, loaded article, preferably dibutyltin dilaurate, butyl titanate, second
The combination of one or both of acyl acetone titanium.
According to the present invention, in the component A, each component has following mass parts ratio:
Hydroxy-end capped 100 mass parts of polysiloxanes, 15~45 mass parts of white carbon black, 0~20 mass parts of silicone resin, resistance to height
Warm 3~20 mass parts of filler.
According to the present invention, in the B component, each component has following mass parts ratio:
100 mass parts of polysilazane, 0.1~2 mass parts of catalyst.
According to the present invention, in the rubber material, component A and component B have following mass parts ratio:
100 mass parts of component A, 3~15 mass parts of B component.
According to the present invention, the organic silicon rubber material can be exemplary by using under the conditions of room temperature curing, high temperature resistant
Ground, at room temperature 3~7 days can completion of cure, can at a high temperature of 350 DEG C 24~72h use；
According to the present invention, the tensile strength of the organic silicon rubber material at room temperature is greater than 2.5MPa, elongation at break
Greater than 190%, adhesive strength is greater than 2.5MPa.
The second aspect of the present invention provides the preparation method of above-mentioned room curing and high temperature resistant silicone rubber material, described
Method includes the following steps:
1) each component for including in above-mentioned component A is mixed, mixed component A is prepared；
2) each component for including in above-mentioned B component is mixed, mixed B component is prepared；
3) in use, the B component of the component A of step 1) and step 2) is mixed, the resistance to height of the room temperature curing is prepared
Warm organic silicon rubber material.
According to the present invention, in step 1), 5min~1h is mixed preferably at 100~160 DEG C.
According to the present invention, in step 1), for example including following steps:
Utilize each component that kneader or planetary mixer (in the way of being suitable for batch production) will include in above-mentioned component A
0.5~1h is mixed at 100~160 DEG C, is kneaded by grinder；Alternatively, will by screw machine (in the way of being suitble to continuous production)
The each component for including in above-mentioned component A mixes 5~15min at 100~160 DEG C, is kneaded by grinder.
According to the present invention, in step 1), the viscosity of the component A has fine at 30000~200000cps (25 DEG C)
Mobility, meet the requirement of various moulding process.
According to the present invention, it in step 2), is mixed preferably by mechanical stirring.
The third aspect of the present invention provides the application of above-mentioned room curing and high temperature resistant silicone rubber material, can make
For resistance to 350 DEG C of elastic adhesive sealing materials, the basis material of resistance to 350 DEG C of elastic thermal protection coatings.
Beneficial effect
1. organic silicon rubber material of the present invention is mutual based on organosilicon macromolecule chain and reinforced filling white carbon black
The mechanism of action, white carbon black after having used the hydroxy-end capped polysiloxanes macromolecule and modification containing different functional groups have
The collaboration reinforcement system of machine silicone resin, and suitable polysilazane curing agent is matched, simplify high temperature resistant elastic adhesive sealing material
Material, elastic coating formula design, reduce use to the huge carbon forming agent of Effect on Mechanical Properties, realize prepare it is high-strength
Degree, room temperature curing, eiastomeric silicone resin resistant to high temperature target, meet requirement.
2. having abandoned high-cost fume colloidal silica in reinforced filling of the invention, use the precipitation method of low cost white
Carbon black, and this precipitated silica makes it contain a large amount of initiation polysiloxane molecule chain degradation because of the essence of its hydrolysis process
Hydroxyl, therefore be not used in the preparation of high temperature resistant polysilane generally.And the present invention is by technological improvement, even if using it is low at
This precipitated silica can also make organic silicon rubber material obtain good high temperature resistance, can tolerate 350 DEG C of high temperature, and
And during the preparation process, additional aftertreatment technology is not needed, so that the preparation process of organic silicon rubber material is easy, is improved
Preparation efficiency reduces production cost.
3. the organic silicon rubber material of room curing and high temperature resistant prepared by the present invention has the function of that good can add again is filled out
The characteristic of material can continue to add required functional filler into the material by certain technique, prepare required resistance to
High temperature, functional elasticity adhering and sealing material and elastic coating material, be such as added the aluminium oxide of high thermal conductivity coefficient, carbon nanotube,
The heat fillings such as carbon black, diamond, metal powder prepare high temperature resistant, high thermal conductivity coating；The graphene etc. that stratiform is added prepares resistance to height
The systems such as temperature, corrosion-resistant finishes, addition hollow glass micro-ball, hollow phenolic aldehyde microballoon, glass fibre, carbon fiber, quartz fibre, aramid fiber
Standby low-density anti-ablation heat resistant coating.
Specific embodiment
As previously mentioned, shown in the structure of the polysilazane such as formula (1):
In formula (1), R1, R2, R3 are identical or different, are independently from each other H, methyl, ethyl, phenyl, vinyl, alkane
One or more, the integer that x, y are 5~1000 of oxygroup, the ratio of x, y are 1:0.2~1.5.
Preferably, the ratio of x, y are 1:0.5~1.2.
Wherein, the polysilazane is prepared by the ammonolysis technique of chlorosilane, and the chlorosilane is trichlorosilane, dichloro
Silane, methyl trichlorosilane, dimethyldichlorosilane, ethyl trichlorosilane, diethyl dichlorosilane, phenyl trichlorosilane, two
Diphenyl dichlorosilane, dichloromethyl phenylsilane, vinyl trichlorosilane, methylvinyldichlorosilane, methyl methoxy base two
Two or more in chlorosilane, methyl ethoxy dichlorosilane etc..
The preparation method of above-mentioned polysilazane, described method includes following steps:
(1) solvent, ammonia, two function chlorosilanes and trifunctional chlorosilane are dried, reaction unit is carried out
It is dried；
(2) solvent of drying process is added in reaction unit by metering pump, by two function chlorine silicon of drying process
Alkane and trifunctional chlorosilane are added in reaction unit by metering pump respectively, and the ammonia of drying process is led to by mass flowmenter
Under the liquid level for entering reaction unit, ammonolysis reaction is carried out；
(3) " slurry " system for containing a large amount of ammonium chlorides after reaction is squeezed by filter device by mortar pump, carried out
It filters and filter residue is washed using solvent, collect filtrate；
(4) being introduced containing the filtrate of polysilazane product by material shifting pump, there is the film of continuous still function to steam
Send out device in, under the vacuum of 50~1000Pa, 50~150 DEG C at a temperature of, the solvent in above-mentioned filtrate is evaporated off, institute is obtained
The polysilazane product needed.
In step (1), the drying process preferably using continuing through the drying modes of molecular sieve absorbents, by solvent,
The water content of ammonia, two function chlorosilanes and trifunctional chlorosilane is controlled in 5ppm hereinafter, wherein molecular sieve is after water suction saturation
It can be regenerated by high temperature sintering.
In step (1), the solvent is that aliphatic hydrocarbon or aromatic hydrocarbon and its any one or two kinds of of corresponding halogenated hydrocarbons mix
Bonding solvent, preferably toluene, petroleum ether, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, glycol dimethyl ether, diethylene glycol dimethyl ether etc..
In step (2), the usage ratio of two function chlorosilanes and trifunctional chlorosilane can pass through the frequency conversion of control metering pump
Device is adjusted, and in 3000~8000rpm, the temperature of reaction unit is controlled at -40~100 DEG C for the speed of agitator control of reaction unit,
The time of ammonolysis reaction be 8~for 24 hours.
In step (2), during ammonolysis reaction, 3~10 ammonias are distributed around agitating shaft preferably in reaction unit
Outlet, and with the pressurized dry air of 1~10MPa, it assists ammonia to generate micro-nano bubble in exit, is strengthened by supercharging air
Ammonia forms micro-nano structure bubble, and then strengthens because the generation of a large amount of ammonium chlorides leads to ammonia in gas-liquid-solid reaction system
Dispersion increases ammonia and chlorosilane contact probability in gas-liquid-solid reaction system, improves reaction efficiency；It is also excellent
It is selected in reaction unit and places a certain number of Ceramic Balls, it is made to collide under the high-speed rotation of agitating device, destroy former
A large amount of ammonium chloride particles that position generates reduce the damage of polysilazane to the cladding of chlorosilane reactant, polysilazane product
It loses, improves reaction yield；Online ammonia detection device is installed in the exhaust outlet of reaction unit, is joined with the mass flowmenter of ammonia
It is dynamic, the uninterrupted of the mass flowmenter of ammonia is adjusted with the ammonia signal strength detected, optimizing process control.Just
It is to be improved based on preparation method, less trifunctional chlorosilane, which can be used, can prepare the poly- silicon with same solidification effect
Azane.Preferably, the control of the mass ratio of the two functions chlorosilane and trifunctional is in 1:0.2~1.5, preferably 1:0.5~1.2.
In step (3), during the filtration process, preferably the filter device with different filtering accuracies carries out multistage-combination, should
Combination unit is able to achieve the filter type of moisture in not ingress of air, the closed material of energy, as filtration washing all-in-one machine, centrifuge are made
For the coarse filter device of the first order, there is the PP cotton of refined filtration effect, ceramic core etc. to be used as second for setting in percolate collection tubes road
The fine filtration device of grade；Observation window is set in percolate collection tubes road, whether is clarified convenient for observation filtrate, if there is muddiness,
It is returned in filter device by the branch in percolate collection tubes road and is filtered again.
In step (4), in distillation process, thin film evaporator is preferably carried out to 2~3 grades of multistage-combination, with continuous
Mode rapid solvent removal, further, the thin film evaporation preferably built in condenser external thin film evaporator and condenser
The multistage-combination of device, wherein afterbody is the thin film evaporator built in condenser.
Further detailed description is done to preparation method of the invention below in conjunction with specific embodiment.It should be appreciated that
The following example is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as limiting the scope of the invention.
In the range of all technologies realized based on above content of the present invention are encompassed by the present invention is directed to protect.
Experimental method used in following embodiments is conventional method unless otherwise specified；
Reagent and material in following embodiments is in addition to the hydroxy-end capped polysiloxanes containing different functional groups is self-control, such as
Without specified otherwise, commercially obtain.
Preparation example 1
The preparation method of hydroxy-terminated polysiloxane containing aminomethyl phenyl: with octamethylcy-clotetrasiloxane, octaphenyl ring four
Siloxanes is raw material, and feed ratio is calculated according to required phenyl content, using tetramethylammonium hydroxide as initiator, is with acetic acid
End-capping reagent preparation.
Preparation example 2
The preparation method of hydroxy-terminated polysiloxane containing methyl ethylene: with octamethylcy-clotetrasiloxane, eight vinyl
Cyclotetrasiloxane is raw material, and feed ratio is calculated according to required contents of ethylene, using tetramethylammonium hydroxide as initiator, with
Acetic acid is end-capping reagent preparation.
Preparation example 3
600L petroleum ether (30~60 DEG C of boiling point) is added after dry through metering pump to the reaction kettle of 1000L by molecular sieve
In, 100kg dimethyldichlorosilane, 100kg methyl trichlorine silicon are added into reaction kettle by the frequency control of metering pump respectively
Alkane starts the stirring of reaction kettle in 5000rpm, controls reactor temperature at -20 DEG C by refrigeration machine, ammonia is passed through molecule
Reaction kettle is entered by mass flowmenter control after sieve is dry, by 5 air inlets of arrangement 3MPa's around agitating shaft
Enter reaction system in a manner of microbubble under air pressure auxiliary, placed 10kg Ceramic Balls in reaction kettle, for breaking original
Cladding of the ammonium chloride that position generates to the poly- methylsilazane of dimethyldichlorosilane, methyl trichlorosilane and generation.Reactant
The logical ammonia of stopping passes through detection of the ammonia at tail gas during this ammonolysis after system can't detect ammonia in tail gas after 24h
The linkage control reaction process of value and ammonia feed rate.Pass through the filtration washing with 400 micron filter cloths after ammonolysis
All-in-one machine filters pressing under the pressure of 0.4MPa is filtered twice by the filter cake of generation using filters pressing again after 300L petroleum ether
The filtrate that obtained filtrate obtains after merging by the fine filtering that 500nmPP cotton carries out the second level.Filtrate is passed through into condenser
External thin film evaporator is under the vacuum degree of 1000Pa, after at room temperature can collecting most of petroleum ether as light component
It recycles, then gained heavy constituent is steamed gently by the thin film evaporator built in condenser under the vacuum degree of 100Pa, at 60 DEG C
The heavy constituent obtained after component is required polysilazane.The viscosity 600cps of products therefrom, yield 82%, molecular weight are
1100。
Embodiment 1
The component A of room curing and high temperature resistant silicone caoutchouc elasticity basis material: weighing molecular weight is 2500, phenyl content
For the 12% hydroxy-end capped polysiloxanes 90kg containing aminomethyl phenyl, weigh that molecular weight is 54000, phenyl content is 6%
Hydroxy-end capped polysiloxanes 10kg containing aminomethyl phenyl is added in planetary mixer, weighs pre- through 4kg hexamethyldisilazane
Precipitated silica (manufacturer is that Fujian is just contained, the trade mark 779) 35kg of processing, the organic siliconresin containing vinyl are (raw
Producing producer is that Jiangxi Xin Jia is virtuous, the trade mark 8206) 5kg, iron oxide 5kg, hydrogeneous carborane 3kg is added in planetary mixer,
It stirs to be kneaded three times on three-roll grinder after 0.5h is mixed at 140 DEG C and obtains required component A material.The viscosity of material is
180000cps (25 DEG C), can use under the operating condition of solvent-free auxiliary.
The B component of room curing and high temperature resistant silicone caoutchouc elasticity basis material: the system that 100kg molecular weight is 1100 is weighed
The polysilazane (wherein: dimethyldichlorosilane 100kg, methyl trichlorosilane 100kg) that the method for standby example 3 is prepared, 1kg
Dibutyltin dilaurate obtains required B component through mechanical stirring after mixing.
It is used after taking above-mentioned two component of A, B to be mixed according to the mass ratio of 100:6 when in use.According to placing at room temperature
Its tensile property, aluminium/aluminium adhesive property are tested after technique solidification in 7 days, the results are shown in Table 1.
Using the organic silicon rubber of the resistance to 350 DEG C of high temperature of prepared room temperature curing as flexible base material (100 mass parts), add
Enter 20 mass parts hollow glass micro-balls (manufacturer is Ma'an Mountain's mine institute, trade mark GS25), 20 mass parts phenolic aldehyde tiny balloons
(manufacturer is Jinan holy well), 5 mass parts glass fibres (manufacturer is Mount Taishan glass, trade mark T435) are after mixing evenly
High temperature heat-resistant protective coating is prepared using room temperature spraying process.Prepared coating be without the use of carbon forming agent in the case where,
Its 350 DEG C ablation mass loss rate 1.4%, the surface after ablation completely, without powder phenomenon-tion occur.
Embodiment 2
The component A of room curing and high temperature resistant silicone caoutchouc elasticity basis material: weighing molecular weight is that 2100, vinyl contains
The hydroxy-end capped polysiloxanes 70kg containing methyl ethylene that amount is 10%, weighs that molecular weight is 58000, contents of ethylene is
The 5% hydroxy-end capped polysiloxanes 30kg containing methyl ethylene is added in planetary mixer, weighs and be through 2kg hydrogen content
The pretreated precipitated silica of 0.8% containing hydrogen silicone oil (manufacturer Luo Diya, the trade mark 142) 25kg contains vinyl
Organic siliconresin 5kg, cerium oxide 5kg, vermiculite 10kg be added planetary mixer in, at 120 DEG C stir 1h mixing after three
It is kneaded three times on roller mill and obtains required component A material.The viscosity of material is 70000cps (25 DEG C), can be solvent-free auxiliary
It is used under the operating condition helped.
The B component of room curing and high temperature resistant silicone caoutchouc elasticity basis material: weigh 100kg molecular weight be 600 it is poly-
(preparation method: dimethyldichlorosilane 100kg, methyl trichlorine 50kg carry out ammonolysis reaction preparation using ammonia to silazane.),
200g stannous octoate obtains required B component through mechanical stirring after mixing.
It is used after taking above-mentioned two component of A, B to be mixed according to the mass ratio of 100:10 when in use.It is transferred according to room temperature
Its tensile property, aluminium/aluminium adhesive property are tested after setting technique solidification in 7 days, the results are shown in Table 1.
Using prepared room curing and high temperature resistant silicone rubber as flexible base material (100 mass parts), 20 matter are added
Amount part hollow glass micro-ball, 20 mass parts phenolic aldehyde tiny balloons, 5 mass parts glass fibres use room temperature to spray work after mixing evenly
Skill prepares high temperature heat-resistant protective coating.Prepared coating is in the case where being without the use of carbon forming agent, 350 DEG C of ablation matter
Amount loss rate 1.2%, the surface after ablation completely, without powder phenomenon-tion occur.
Embodiment 3
The component A of room curing and high temperature resistant silicone caoutchouc elasticity basis material: weighing molecular weight is that 6000, vinyl contains
The hydroxy-end capped polysiloxanes 80kg containing methyl ethylene that amount is 12%, weighing molecular weight is 80000 methylic hydroxyls
Polysiloxanes (manufacturer is Jiangxi spark, the trade mark 107) 20kg of sealing end, is added in planetary mixer, weighs and contain through 2kg
The pretreated precipitated silica of vinyl silicone oil that ethylene base unit weight is 2% (manufacturer is Fujian Far Glory, the trade mark 900)
20kg, the organic siliconresin 20kg containing vinyl, zinc oxide 10kg, 5kg containing ethenyl cage model sesquialter siloxane addition planet stir
It mixes in machine, is kneaded three times on three-roll grinder after stirring 2h mixing at 190 DEG C and obtains required component A material.Material
Viscosity is 50000cps, can be used under the operating condition of solvent-free auxiliary.
The B component of room curing and high temperature resistant silicone caoutchouc elasticity basis material: weigh 100kg molecular weight be 1500 it is poly-
(preparation method: dimethyldichlorosilane 100kg, methyl trichlorine 120kg carry out ammonolysis reaction preparation using ammonia to silazane.),
2kg titanium acetylacetone obtains required B component through mechanical stirring after mixing.
It is used after taking above-mentioned two component of A, B to be mixed according to the mass ratio of 100:15 when in use.It is transferred according to room temperature
Its tensile property, aluminium/aluminium adhesive property are tested after setting technique solidification in 7 days, the results are shown in Table 1.
Using prepared room curing and high temperature resistant silicone rubber as flexible base material (100 mass parts), 20 matter are added
Amount part hollow glass micro-ball, 20 mass parts phenolic aldehyde tiny balloons, 5 mass parts glass fibres use room temperature to spray work after mixing evenly
Skill prepares high temperature heat-resistant protective coating.Prepared coating is in the case where being without the use of carbon forming agent, 350 DEG C of ablation matter
Amount loss rate 1.1%, the surface after ablation completely, without powder phenomenon-tion occur.
Embodiment 4
The component A of room curing and high temperature resistant silicone caoutchouc elasticity basis material: weighing molecular weight is 3000, phenyl content
For the 15% hydroxy-end capped polysiloxanes 90kg containing aminomethyl phenyl, weigh molecular weight be 60000, contents of ethylene 8%
The hydroxy-end capped polysiloxanes 10kg containing methyl ethylene, be added in planetary mixer, weigh and be through 3kg base unit weight containing ethylene
6% vinyl silicone oil pretreated precipitated silica 15kg, the organic siliconresin 15kg containing ethenylphenyl, iron oxide
5kg, sepiolite 3kg, silicon nitride 10kg are added in planetary mixer, are stirred after 0.5h is mixed at 140 DEG C in three-roll grinder
Upper be kneaded three times obtains required component A material.The viscosity of material is 110000cps, can be made under the operating condition of solvent-free auxiliary
With.
The B component of room curing and high temperature resistant silicone caoutchouc elasticity basis material: weigh 100kg molecular weight be 1900 it is poly-
(preparation method: dimethyldichlorosilane 100kg, methyl trichlorine 150kg carry out ammonolysis reaction preparation using ammonia to silazane.),
2kg dibutyltin dilaurate obtains required B component through mechanical stirring after mixing.
It is used after taking above-mentioned two component of A, B to be mixed according to the mass ratio of 100:10 when in use.It is transferred according to room temperature
Its tensile property, aluminium/aluminium adhesive property are tested after setting technique solidification in 7 days, the results are shown in Table 1.
Using prepared room curing and high temperature resistant silicone rubber as flexible base material (100 mass parts), 20 matter are added
Amount part hollow glass micro-ball, 20 mass parts phenolic aldehyde tiny balloons, 5 mass parts glass fibres use room temperature to spray work after mixing evenly
Skill prepares high temperature heat-resistant protective coating.Prepared coating is in the case where being without the use of carbon forming agent, 350 DEG C of ablation matter
Amount loss rate 1.5%, the surface after ablation completely, without powder phenomenon-tion occur.
Comparative example 1
The component A of room curing and high temperature resistant silicone caoutchouc elasticity basis material: weighing molecular weight is 2500, phenyl content
For the 12% hydroxy-end capped polysiloxanes 90kg containing aminomethyl phenyl, weigh that molecular weight is 54000, phenyl content is 6%
Hydroxy-end capped polysiloxanes 10kg containing aminomethyl phenyl is added in planetary mixer, weighs untreated precipitation method hard charcoal
Black 35kg, the organic siliconresin 5kg containing vinyl, iron oxide 5kg, hydrogeneous carborane 3kg is added in planetary mixer, 140
It stirs to be kneaded three times on three-roll grinder after 0.5h is mixed at DEG C and obtains required component A material.The viscosity of material is
600000cps agglomerates after placing 5 days, can not further use.
The introducing for illustrating untreated precipitated silica causes the processing performance of hydroxy-end capped polysiloxanes to become
Difference, and when storing 5 days, serious " structuring ", which occurs, for prepared component A causes to agglomerate, even if after the completion of preparation immediately
It uses, needing additionally to be added 5 times of hexamethylene dilution could construct reluctantly, and 20 mass parts hollow glass micro-balls, 20 matter are being added
Mass loss of the coating prepared after amount part phenolic aldehyde tiny balloon, 5 mass parts glass fibres at 350 DEG C is 12%, and is gone out
It cracks on existing surface.
Comparative example 2
The component A of room curing and high temperature resistant silicone caoutchouc elasticity basis material: weighing molecular weight is 4000 containing 100%
The hydroxy-end capped polysiloxanes 90kg of methyl weighs the hydroxy-end capped poly- silicon oxygen containing 100% methyl that molecular weight is 50000
Alkane 10kg is added in planetary mixer, weighs the pretreated precipitated silica 35kg of 4kg hexamethyldisilazane, contains ethylene
The organic siliconresin 5kg of base, iron oxide 5kg, hydrogeneous carborane 3kg are added in planetary mixer, and it is mixed that 0.5h is stirred at 140 DEG C
It is kneaded three times on three-roll grinder after conjunction and obtains required component A material.The viscosity of material is 190000cps, can be without molten
It is used under the operating condition of agent auxiliary.
The B component of room curing and high temperature resistant silicone caoutchouc elasticity basis material: weigh 100kg molecular weight be 1100 it is poly-
Silazane, 1kg dibutyltin dilaurate obtain required B component through mechanical stirring after mixing.
It is used after taking above-mentioned two component of A, B to be mixed according to the mass ratio of 100:6 when in use.According to placing at room temperature
Its tensile property, aluminium/aluminium adhesive property are tested after technique solidification in 7 days, the results are shown in Table 1.
Using prepared room curing and high temperature resistant silicone rubber as flexible base material (100 mass parts), 20 matter are added
Amount part hollow glass micro-ball, 20 mass parts phenolic aldehyde tiny balloons, 5 mass parts glass fibres use room temperature to spray work after mixing evenly
Skill prepares high temperature heat-resistant protective coating.Prepared coating is in the case where being without the use of carbon forming agent, 350 DEG C of ablation matter
Amount loss rate 5.4%, the surface dusting after ablation are serious.
Illustrate, when selecting the hydroxy-end capped polysiloxanes for containing 100% methyl, the organic silicon rubber material that is prepared
It can not provide blocking required " carbon source " at high temperature, and be difficult to ensure organic silicon rubber material in the case where not using carbon forming agent
The moulding processability and mechanical behavior under high temperature of material.
Comparative example 3
The component A of room curing and high temperature resistant silicone caoutchouc elasticity basis material: weighing molecular weight is 2500, phenyl content
For the 12% hydroxy-end capped polysiloxanes 90kg containing aminomethyl phenyl, weigh that molecular weight is 54000, phenyl content is 6%
Hydroxy-end capped polysiloxanes 10kg containing aminomethyl phenyl is added in planetary mixer, weighs pre- through 4kg hexamethyldisilazane
Row is added in the precipitated silica 35kg of processing, the organic siliconresin 5kg containing vinyl, iron oxide 5kg, hydrogeneous carborane 3kg
In star blender, it is kneaded three times on three-roll grinder after stirring 0.5h mixing at 140 DEG C and obtains required component A material.
The viscosity of material is 180000cps (25 DEG C), can be used under the operating condition of solvent-free auxiliary.
The B component of room curing and high temperature resistant silicone caoutchouc elasticity basis material: 100kg ethyl orthosilicate, 1kg bis- are weighed
Butyl tin dilaurate obtains required B component through mechanical stirring after mixing.
It is used after taking above-mentioned two component of A, B to be mixed according to the mass ratio of 100:6 when in use.According to placing at room temperature
Its tensile property, aluminium/aluminium adhesive property are tested after technique solidification in 7 days, the results are shown in Table 1.
Using prepared organic silicon rubber as flexible base material, 20 mass parts hollow glass micro-balls, 20 mass parts are added
Phenolic aldehyde tiny balloon, 5 mass parts glass fibres prepare thermal protection coating using room temperature spraying process after mixing evenly.It is prepared
Coating be without the use of carbon forming agent in the case where, 350 DEG C of ablation mass loss rate 24%, the serious powder in surface after ablation
Change, a large amount of hole occurs.
The performance of the organic silicon rubber material of the resistance to 350 DEG C of high temperature of 1 room temperature curing of table
| Serial number | Tensile strength/MPa | Elongation at break/% | Adhesive strength/MPa | 350 DEG C of weightlessness/% |
| Embodiment 1 | 3.0 | 210 | 2.7 | 1.4 |
| Embodiment 2 | 3.1 | 190 | 2.8 | 1.2 |
| Embodiment 3 | 2.7 | 220 | 3.0 | 1.1 |
| Embodiment 4 | 2.5 | 210 | 2.8 | 1.5 |
| Comparative example 1 | 1.4 | 120 | 1.5 | 12 |
| Comparative example 2 | 2.1 | 195 | 2.3 | 5.4 |
| Comparative example 3 | 2.6 | 180 | 2.5 | 24 |
As can be seen that the organic silicon rubber material that the application is prepared not only has preferable mechanics from above-mentioned table 1
Performance is also resistant to 350 DEG C of high temperature.
Claims (10)
1. a kind of room curing and high temperature resistant silicone rubber material, wherein the rubber material includes sizing component A, hands over
Join curing agent B component, wherein component A includes: basic glue, white carbon black, high temperature resistant additive, and the basis glue is hydroxy-end capped
Polysiloxanes；B component includes polysilazane, catalyst；
The hydroxy-end capped polysiloxanes has the following structure:
Wherein, R1And R2It is identical or different, it is independently from each other methyl, ethyl, phenyl, vinyl, itrile group, trifluoro propyl, nitrile
Propyl, and it is not simultaneously selected from methyl；X and y is the integer between 0~1000, and is not simultaneously 0.
2. organic silicon rubber material according to claim 1, wherein x and y is the integer between 20~700.
Preferably, the molecular weight of the polysiloxanes is 1000~100000, and preferred molecular weight is 2000~60000.
3. organic silicon rubber material according to claim 1 or 2, wherein in the component A, hydroxy-end capped poly- silicon oxygen
Alkane can be single polysiloxanes, be also possible to two or more different structure, different molecular weight polysiloxanes into
Row matching uses, wherein hydroxy-end capped polysiloxanes dosage of the molecular weight in 1000~10000 ranges is in 60~100 matter
Measure part, the dosage of the hydroxy-end capped polysiloxanes of preferably 70~90 mass parts, molecular weight in 20000~100000 ranges
For 40~0 mass parts, preferably 30~10 mass parts.
Preferably, in the component A, white carbon black is modified dose of treated white carbon black.For example, modified dose treated
The obtained white carbon black prepared by the precipitation method.
The modifying agent is silazane or silicone compounds, for example, 3wt%~10wt% one of following modifying agent or
Two or more combinations: hexamethyldisilazane, hydrogen containing siloxane, hydrogeneous polysilazane, contains second at hexamethyl cyclotrisilazane
Alkenyl polysiloxanes, polysilazane containing vinyl, octamethylcy-clotetrasiloxane, hydroxyl polysiloxanes.
Preferably, in the component A, high temperature resistant additive is selected from iron oxide, iron hydroxide, ferric oxalate, alkoxy iron, organosilicon
Ferrocene, titanium oxide, zinc oxide, zinc carbonate, cerium oxide, vermiculite, sepiolite, cagelike structure silsesquioxane, carborane (such as contain
Hydrogen carborane), a combination of one or more of silicon nitride, silicon carbide, boron nitride etc..
4. organic silicon rubber material according to claim 1-3, wherein in the component A, further comprise as
The organic siliconresin containing D, T, Q structure of lower group end capping: one in hydrogen, methyl, vinyl, phenyl, methoxyl group and ethyoxyl
Kind or two kinds.
5. organic silicon rubber material according to claim 1-4, wherein in the B component, polysilazane conduct
Room temperature curing agent uses.
Preferably, the viscosity of the polysilazane is 200~2000cps, preferably 500~1500cps.
Preferably, the molecular weight of the polysilazane is 200~60000, preferably 500~15000.
Preferably, shown in the structure of the polysilazane such as formula (1):
In formula (1), R1, R2, R3 are identical or different, are independently from each other H, methyl, ethyl, phenyl, vinyl, alkoxy
One or more, the integer that x, y are 5~1000, the ratio of x, y is 1:0.2~1.5.
Preferably, the ratio of x, y are 1:0.5~1.2.
Preferably, the polysilazane is prepared by the ammonolysis technique of chlorosilane, and the chlorosilane is trichlorosilane, dichloro silicon
Alkane, methyl trichlorosilane, dimethyldichlorosilane, ethyl trichlorosilane, diethyl dichlorosilane, phenyl trichlorosilane, hexichol
Base dichlorosilane, dichloromethyl phenylsilane, vinyl trichlorosilane, methylvinyldichlorosilane, methyl methoxy base dichloro
Two or more in silane, methyl ethoxy dichlorosilane etc..
Preferably, in the B component, catalyst is combined selected from one or both of organotin or organic titanium compound,
For example, dibutyltin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tins, dibutyltin diacetate, dioxane
Base tin dimaleate, two mercaptan tin alkyls, mercaptan dioctyl tin, butyl titanate, the metatitanic acid tert-butyl ester, titanium acetylacetone etc.
Single compound or its chelate, loaded article, preferably dibutyltin dilaurate, butyl titanate, in titanium acetylacetone
One or two kinds of combinations.
6. organic silicon rubber material according to claim 1-5, wherein in the component A, each component has such as
Lower mass parts ratio:
Hydroxy-end capped 100 mass parts of polysiloxanes, 15~45 mass parts of white carbon black, 0~20 mass parts of silicone resin, high temperature resistant are filled out
Expect 3~20 mass parts.
Preferably, in the B component, each component has following mass parts ratio:
100 mass parts of polysilazane, 0.1~2 mass parts of catalyst.
Preferably, in the rubber material, component A and component B have following mass parts ratio:
100 mass parts of component A, 3~15 mass parts of B component.
7. organic silicon rubber material according to claim 1-6, wherein the organic silicon rubber material can pass through
Used under the conditions of room temperature curing, high temperature resistant, illustratively, at room temperature 3~7 days can completion of cure, can be in 350 DEG C of high temperature
Lower 24~72h is used；
Preferably, the tensile strength of the organic silicon rubber material at room temperature is greater than 2MPa, elongation at break is greater than 150%,
Adhesive strength is greater than 2MPa.
8. the preparation method of any one of the claim 1-7 room curing and high temperature resistant silicone rubber material, the method packet
Include following steps:
1) each component for including in above-mentioned component A is mixed, mixed component A is prepared；
2) each component for including in above-mentioned B component is mixed, mixed B component is prepared；
3) in use, the B component of the component A of step 1) and step 2) is mixed, the room curing and high temperature resistant, which is prepared, to be had
Machine silastic material.
9. preparation method according to claim 8, wherein in step 1), preferably at 100~160 DEG C mix 5min~
1h。
Preferably, in step 1), include the following steps: to utilize kneader or planetary mixer (in the way of being suitable for batch production)
The each component for including in above-mentioned component A is mixed into 0.5~1h at 100~160 DEG C, is kneaded by grinder；Alternatively, utilizing spiral shell
The each component for including in above-mentioned component A is mixed 5~15min by bar machine (being suitble to continuous production mode) at 100~160 DEG C, after
Ground machine is kneaded.
10. the application of any one of the claim 1-7 room curing and high temperature resistant silicone rubber material, can be used as resistance to
The basis material of 350 DEG C of elastic adhesive sealing materials, resistance to 350 DEG C of elastic thermal protection coatings.
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| CN110373904A (en) * | 2019-07-01 | 2019-10-25 | 海瑞可（武汉）新材料有限公司 | A kind of synthetic fibers microstructural flaws restorative procedure and high strength synthetic fibre rope |
| CN110484197A (en) * | 2019-08-23 | 2019-11-22 | 武汉双键开姆密封材料有限公司 | A kind of preparation method of room curing and high temperature resistant silicone adhesives |
| CN111320966A (en) * | 2020-04-10 | 2020-06-23 | 深圳深汕特别合作区昌茂粘胶新材料有限公司 | Novel high-temperature-resistant adhesive and preparation method thereof |
| CN111500188A (en) * | 2020-05-26 | 2020-08-07 | 上海灿达建材科技有限公司 | Water-based siloxane coating for outdoor building and preparation process thereof |
| CN111793462A (en) * | 2020-07-20 | 2020-10-20 | 广州市白云化工实业有限公司 | Silicone sealant for rail transit and preparation method thereof |
| CN112080248A (en) * | 2020-09-24 | 2020-12-15 | 中山沃硅化工科技有限公司 | Composite flame-retardant insulating electronic sealant and preparation method thereof |
| CN112251029A (en) * | 2020-10-21 | 2021-01-22 | 佛山科学技术学院 | Tracking-resistant silicone rubber and preparation method and application thereof |
| CN112552726A (en) * | 2020-12-14 | 2021-03-26 | 福建鸣友新材料科技有限公司 | Heat-resistant coating material for thermal transfer ribbon and preparation method and use method thereof |
| CN112812308A (en) * | 2020-12-30 | 2021-05-18 | 浙江艾特普科技有限公司 | Organic silicon modified PAE resin, preparation method and A-type flame-retardant coating thereof |
| CN113388120A (en) * | 2021-06-16 | 2021-09-14 | 山东省科学院新材料研究所 | High-heat-resistance copolymer silicone resin and preparation method thereof |
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| CN114316890A (en) * | 2021-12-24 | 2022-04-12 | 山东工业陶瓷研究设计院有限公司 | Silicone rubber binder and preparation method and application thereof |
| CN114561149A (en) * | 2022-03-11 | 2022-05-31 | 江西师范大学 | Superhard polysilazane easy-to-clean coating and preparation method thereof |
| WO2022111288A1 (en) * | 2020-11-30 | 2022-06-02 | 北京宇航系统工程研究所 | Weather-resistant silazane rubber with three-dimensional network structure and preparation method therefor |
| CN114933806A (en) * | 2022-06-21 | 2022-08-23 | 广东艾默森科技有限公司 | Preparation method of polymer-based waterproof flame-retardant high-temperature-resistant insulating material |
| CN115073750A (en) * | 2022-06-17 | 2022-09-20 | 中国科学院长春应用化学研究所 | Humidity-heat-resistant room-temperature curing silicone rubber and preparation method thereof |
| CN115216017A (en) * | 2021-04-21 | 2022-10-21 | 中国科学院化学研究所 | Preparation method and application of alkoxy polysilazane |
| CN115286995A (en) * | 2022-06-29 | 2022-11-04 | 上海航天化工应用研究所 | High-performance heat-proof coating based on interpenetrating network structure and preparation method thereof |
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Cited By (33)
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| CN110373904A (en) * | 2019-07-01 | 2019-10-25 | 海瑞可（武汉）新材料有限公司 | A kind of synthetic fibers microstructural flaws restorative procedure and high strength synthetic fibre rope |
| CN110484197B (en) * | 2019-08-23 | 2021-05-14 | 武汉双键开姆密封材料有限公司 | Preparation method of room-temperature-cured high-temperature-resistant organic silicon adhesive |
| CN110484197A (en) * | 2019-08-23 | 2019-11-22 | 武汉双键开姆密封材料有限公司 | A kind of preparation method of room curing and high temperature resistant silicone adhesives |
| CN111320966A (en) * | 2020-04-10 | 2020-06-23 | 深圳深汕特别合作区昌茂粘胶新材料有限公司 | Novel high-temperature-resistant adhesive and preparation method thereof |
| CN111500188A (en) * | 2020-05-26 | 2020-08-07 | 上海灿达建材科技有限公司 | Water-based siloxane coating for outdoor building and preparation process thereof |
| CN111793462A (en) * | 2020-07-20 | 2020-10-20 | 广州市白云化工实业有限公司 | Silicone sealant for rail transit and preparation method thereof |
| CN112080248A (en) * | 2020-09-24 | 2020-12-15 | 中山沃硅化工科技有限公司 | Composite flame-retardant insulating electronic sealant and preparation method thereof |
| CN112080248B (en) * | 2020-09-24 | 2022-05-17 | 中山沃硅化工科技有限公司 | Composite flame-retardant insulating electronic sealant and preparation method thereof |
| CN112251029A (en) * | 2020-10-21 | 2021-01-22 | 佛山科学技术学院 | Tracking-resistant silicone rubber and preparation method and application thereof |
| WO2022111288A1 (en) * | 2020-11-30 | 2022-06-02 | 北京宇航系统工程研究所 | Weather-resistant silazane rubber with three-dimensional network structure and preparation method therefor |
| CN112552726A (en) * | 2020-12-14 | 2021-03-26 | 福建鸣友新材料科技有限公司 | Heat-resistant coating material for thermal transfer ribbon and preparation method and use method thereof |
| CN112812308A (en) * | 2020-12-30 | 2021-05-18 | 浙江艾特普科技有限公司 | Organic silicon modified PAE resin, preparation method and A-type flame-retardant coating thereof |
| CN115216017B (en) * | 2021-04-21 | 2023-09-15 | 中国科学院化学研究所 | Preparation method and application of alkoxy polysilazane |
| CN115216017A (en) * | 2021-04-21 | 2022-10-21 | 中国科学院化学研究所 | Preparation method and application of alkoxy polysilazane |
| CN113388120B (en) * | 2021-06-16 | 2022-07-12 | 山东省科学院新材料研究所 | High-heat-resistance copolymer silicone resin and preparation method thereof |
| CN113388120A (en) * | 2021-06-16 | 2021-09-14 | 山东省科学院新材料研究所 | High-heat-resistance copolymer silicone resin and preparation method thereof |
| CN113980639A (en) * | 2021-11-02 | 2022-01-28 | 绵阳惠利电子材料有限公司 | Transparent and flowing packaging material capable of being rapidly cured at room temperature and preparation method thereof |
| CN114316890A (en) * | 2021-12-24 | 2022-04-12 | 山东工业陶瓷研究设计院有限公司 | Silicone rubber binder and preparation method and application thereof |
| CN114561149A (en) * | 2022-03-11 | 2022-05-31 | 江西师范大学 | Superhard polysilazane easy-to-clean coating and preparation method thereof |
| CN115073750A (en) * | 2022-06-17 | 2022-09-20 | 中国科学院长春应用化学研究所 | Humidity-heat-resistant room-temperature curing silicone rubber and preparation method thereof |
| CN115073750B (en) * | 2022-06-17 | 2023-03-14 | 中国科学院长春应用化学研究所 | Humidity-heat-resistant room-temperature curing silicone rubber and preparation method thereof |
| CN114933806A (en) * | 2022-06-21 | 2022-08-23 | 广东艾默森科技有限公司 | Preparation method of polymer-based waterproof flame-retardant high-temperature-resistant insulating material |
| CN115286995A (en) * | 2022-06-29 | 2022-11-04 | 上海航天化工应用研究所 | High-performance heat-proof coating based on interpenetrating network structure and preparation method thereof |
| CN115286995B (en) * | 2022-06-29 | 2023-09-29 | 上海航天化工应用研究所 | High-performance heat-resistant coating based on interpenetrating network structure and preparation method thereof |
| CN115851127B (en) * | 2022-11-30 | 2023-08-25 | 湖南弘辉科技有限公司 | High-temperature-resistant thermal-insulation coating for missile wing, preparation method of high-temperature-resistant thermal-insulation coating and missile wing |
| CN115851127A (en) * | 2022-11-30 | 2023-03-28 | 湖南弘辉科技有限公司 | Missile wing high-temperature-resistant heat-insulating coating, preparation method thereof and missile wing |
| CN115820200A (en) * | 2022-12-07 | 2023-03-21 | 中国航发动力股份有限公司 | Coating method of high-temperature component joint surface sealant |
| CN115948117A (en) * | 2023-02-20 | 2023-04-11 | 江苏纳恩新材料有限公司 | High-wear-resistance organic silicon coating for synthetic leather and preparation method thereof |
| CN116239951A (en) * | 2023-04-19 | 2023-06-09 | 北京工业大学 | Modified silicone rubber coating material and preparation method thereof |
| CN117659862A (en) * | 2023-12-18 | 2024-03-08 | 北京和尔泰新材料科技有限公司 | High-temperature-resistant protective coating and preparation and use methods thereof |
| CN117659862B (en) * | 2023-12-18 | 2024-07-16 | 北京和尔泰新材料科技有限公司 | High-temperature-resistant protective coating and preparation and use methods thereof |
| CN118006280A (en) * | 2024-04-08 | 2024-05-10 | 山东广亚新材料有限公司 | Organosilicon modified polyurethane sealant |
| CN118006280B (en) * | 2024-04-08 | 2024-07-02 | 山东广亚新材料有限公司 | Organosilicon modified polyurethane sealant |
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